CN106573945B - Hybrid fire retardant based on DOPO - Google Patents

Abstract

The present invention relates to novel and improved halogen-free flame retardant compounds having the structure of formula (I): wherein: R ¹ and R ² are independently hydrogen, C ₁ -C ₆ alkyl, -P(O)( OR ³ ) ₂ , -P(O)OR ³ R ⁴ , -P(O)R ³ ₂ , wherein R ³ and R ⁴ are independently C ₁ -C ₄ alkyl, C ₆ -C ₁₂ aryl, C ₇ -C ₁₅ aralkyl group or C ₇ -C ₁₅ alkaryl group; or R ¹ and R ² together form an unsaturated cyclic ring, which is optionally substituted with an alkyl group; each k is independently an integer from 1 to 2 each X is independently oxygen (O) or sulfur (S); v is 0 or 1; each Y is independently C ₁ -C ₄ alkylene, C ₆ arylene, C ₇ -C ₁₅ arylene base, C ₇ -C ₁₅ alkylene aryl, oxygen (O), nitrogen (NR), wherein R is H or C ₁ -C ₄ alkyl; n is 0, 1 or 2, provided that when Y is oxygen ( n is 1 for O) or nitrogen (NR); each Z is independently C ₁ -C ₄ alkylene, C ₆ arylene, C ₇ -C ₁₅ aralkylene or C ₇ -C ₁₅ alkylene arylene m is independently 0, 1 or 2; provided that m cannot be 0 when Y is oxygen (O) or nitrogen (N); each Q is independently a C ₁ -C ₄ alkylene; t is 1 to An integer of 2; W is oxygen (O) or sulfur (S). This compound is particularly suitable as a flame retardant additive for thermoplastic polyesters.

Description

Hybrid flame retardant based on DOPO

technical field

The present invention generally relates to novel flame retardant 9,10-dihydro-9-oxa-10-phosphaphenanthrene compounds.

Background technique

Various phosphorus-containing compounds have been investigated for their suitability as flame retardant additives. In particular, DOPO (9,10-dihydro-9-oxa-phosphaphenanthrene-10-oxide) and its derivatives have been explored as flame retardants and are known to act mainly through a gas phase flame retardant mechanism .

For example, it is known from EP 1506968 that DOPO-based phosphonates can be efficiently synthesized, while US4228064 demonstrates the utility of DOPO-based phosphonates and phosphites as flame retardant additives for polyphenylene ether formulations. Furthermore, EP2557085 describes the synthesis of DOPO-based phosphonamidates and their use in polyurethane foams.

Furthermore, it is known from DE 10330774 and EP 2284208 that DOPO can be reacted with unsaturated dicarboxylic acids and subsequently copolymerized with other P-containing derivatives suitable for establishing ester bonds in order to obtain flame-retardant polymers with different P contents ester. These DOPO-based polymers can be used, for example, as flame retardant additives for polyethylene terephthalate (PET) in fiber applications, or as stand-alone flame retardant polyesters in engineering plastics.

Although the thermal stability of some of the reported DOPO derivatives enables them to be melt processed at elevated temperatures as commonly used for polyester processing, none of these derivatives have been shown to form char upon pyrolysis (char) (this is a property that will increase their efficacy as flame retardant additives).

Polymers and/or oligomers containing pentaerythritol diphosphonates (carbon precursor units), with DOPO as pendant groups (usually no molecular weights are reported) are known, as e.g. Wang X. et al. in Materials Chemistry and Physics 2011, 125, 536- 541 Medium. However, for all reported structures, the problem of having halogenated end groups is not addressed. This can be a problem due to the fact that for relatively low molecular weight additives the importance of end groups increases.

Pentaerythritol phosphate alcohol (PEPA) is known as a flame retardant additive which has relatively low thermal stability (decomposition around 200°C), acts mainly as a coacervate phase, and forms up to 40% by weight on pyrolysis. carbon. Derivatives of PEPA are mainly used as flame retardant additives for polyolefins such as polypropylene, as described in US5420326.

US 4801625 describes PEPA derivatives which in combination with other polymer additives such as inert gas generating compounds such as melamine or other phosphorus containing derivatives such as ammonium polyphosphate make polyolefins flame retardant. WO 91/04295 teaches the use of PEPA derivatives for obtaining smoke suppressed unsaturated polyester resin compositions.

SUMMARY OF THE INVENTION

Probably, one of the most important classes of synthetic polymers requiring flame resistance are thermoplastic polyesters, which have many applications such as engineering plastics and melt-spun fibers. Any flame retardant additive to be added to such a polymer should have sufficient thermal stability to withstand the temperatures typically required for melt processing of the polymer. Accordingly, there remains a need for new and improved halogen-free flame retardants for thermoplastics processed at high temperatures. Such compounds should be effective in their flame retardant effect and should not adversely affect the desired properties of the polymer matrix such as melt viscosity (processability), mechanical properties or the ability to melt spin fibers.

According to one aspect of the present invention, there is provided a flame retardant compound having the structure of formula (I):

wherein R ¹ and R ² can be independently hydrogen, C ₁ -C ₆ alkyl, -P(O)(OR ³ ) ₂ , -P(O)OR ³ R ⁴ , -P(O)R ³ ₂ , wherein R ³ and R ⁴ can be independently C ₁ -C ₄ alkyl, C ₆ -C ₁₂ aryl, C ₇ -C ₁₅ aralkyl, C ₇ -C ₁₅ alkaryl; or R ¹ and R ² taken together can form an unsaturated cyclic ring, which can be substituted with an alkyl group; each k can be independently an integer from 1 to 2; each X can be independently oxygen (O) or sulfur (S); v can be 0 or 1; each Y can be independently C ₁ -C ₄ alkylene, C ₆ arylene, C ₇ -C ₁₅ aralkylene, C ₇ -C ₁₅ alkylene, oxygen (O), nitrogen (NR), wherein R is H or _C1 - _C4 alkyl; n can be 0, 1, or 2, provided that n is 1 when Y is oxygen (O) or nitrogen (NR); each Z can be independently is C ₁ -C ₄ alkylene, C ₆ arylene, C ₇ -C ₁₅ aralkylene, or C ₇ -C ₁₅ alkylene; m can be independently 0, 1, or 2; provided that when When Y is oxygen (O) or nitrogen (N), m cannot be 0; each Q can be independently C ₁ -C ₄ alkylene; t is an integer from 1 to 2; W can be oxygen (O) or sulfur ( S).

Advantageous embodiments of the invention are defined in the dependent claims and/or described herein below.

Surprisingly it has been found that the compounds defined above, which are based on a combination of DOPO- and PEPA-type moieties, and can therefore be conceived as "hybrid flame retardants", appear to be useful in flame retardant compounds, in particular for use in thermoplastic polymers. A combination of several properties that are highly desirable in flame retardant additives for esters. Such advantageous properties include, but are not limited to: high thermal stability (enabling melt blending), high melt temperatures of at least about 150°C and slightly lower than the melt processing temperature of most polyesters, allowing the additive to be used in More uniform dispersion in the polymer matrix.

Preferably, the thermal stability of the compound is from about 270°C to about 335°C, more preferably from about 280°C to about 330°C, most preferably from about 290°C to about 325°C, and the melting temperature is preferably from about 150°C to about 260°C, more preferably from about 160°C to about 240°C, most preferably from about 170°C to about 230°C. The compounds of the present invention exhibit hybrid flame retardant activity both in the gas phase and in the condensed phase when exposed to flame or fire. In other words, different flame retardant mechanisms are combined in one molecule and thus can be included in the polymer without mixing two different flame retardant compounds.

It is contemplated that the compounds of the present invention may be useful for improving the flame resistance of certain thermoset polymers.

In particular, however, the compounds of the present invention are useful for making thermoplastic polyester materials which have good flame resistance despite relatively low additive loadings.

Accordingly, in accordance with another aspect of the present invention, there is provided a polymeric material having improved flame resistance (hereinafter also referred to as "flammable polymeric material") comprising at least one thermoplastic polymer resin and at least one having properties such as A flame retardant compound of the structure of formula (I) as defined above, and optionally comprising any conventional additives.

In some embodiments, the thermoplastic polymer resin may be a polyolefin, polycarbonate, or epoxy resin. According to another embodiment, the thermoplastic polymer resin is a polyester resin.

According to one embodiment, the flame retardant polymer material may additionally comprise a nitrogen-based flame retardant agent as a second flame retardant ingredient.

According to one embodiment, the polymeric material is in a form suitable for engineering plastics applications. According to another embodiment, the polymeric material is in fiber form (especially for textile applications).

Hereinafter, the term "radical" is sometimes used interchangeably with "group" or "moiety" or "substituent", eg "alkyl radical" is equivalent to as commonly used in organic chemistry "Alkyl group".

Unless otherwise specified, the term "alkyl" as used herein includes saturated monovalent hydrocarbon radicals having straight or branched chain moieties such as, but not limited to, methyl, ethyl, propyl, isopropyl, butyl or isobutyl.

Unless otherwise specified, the term "alkylene" as used herein includes saturated divalent hydrocarbon radicals having straight or branched chain moieties such as, but not limited to, methylene, ethylene, propylene, isomethylene propyl, butylene or isobutylene.

Unless otherwise specified, the term "aryl" as used herein includes aromatic radicals derived from aromatic hydrocarbons by removal of one hydrogen, such as, but not limited to, phenyl or naphthyl.

Unless otherwise specified, the term "arylene" as used herein includes aromatic divalent radicals derived from aromatic hydrocarbons by removal of two hydrogens, such as, but not limited to, phenylene.

Unless otherwise specified, the term "aralkyl" as used herein refers to an "arylalkyl" group such as, but not limited to, benzyl ( _{C6H5 -} CH2-) or methylbenzyl ( _{CH3- )} -C ₆ H ₄ -CH ₂ -).

Unless otherwise specified, the term "alkaryl" as used herein refers to an "alkylaryl" group such as, but not limited to, methylphenyl ( _{CH3 - C6H4-} ), dimethylphenyl ((CH ₃ ) ₂ -C ₆ H ₃ -) or isopropylphenyl ((CH ₃ ) ₂ CC ₆ H ₄ -).

Unless otherwise specified, the term "thermal stability" as used herein with respect to a compound is characterized as indicating a "decomposition temperature", which should be understood as the threshold at which significant (5% weight loss in inert atmosphere) thermal decomposition of the compound begins temperature.

In one embodiment of the flame retardant compound, both n and m are 0, X is independently oxygen (O) or sulfur (S), Q is methylene ( _-CH2- ), t is 1, W is oxygen (O). In another embodiment, both R ¹ and R ² are independently hydrogen or C ₁ -C ₆ alkyl. In another embodiment, Y is methylene ( _-CH2- ), n is 1, m is 0, X is oxygen (O), Q is methylene ( _-CH2- ), t is 1, W is oxygen (O). In yet another embodiment, X is independently oxygen (O) or sulfur (S), Y is oxygen (-O-) or nitrogen (-NH-), n is 1, and Z is methylene ( _-CH2) . -), m is 2, Q is methylene ( _-CH2- ), t is 1, and W is oxygen (O).

Specific examples of compounds of formula (I) useful in the present invention are:

According to another aspect, a method of making a hybrid flame retardant compound of formula (I) comprises reacting a compound of formula (A) with a compound of formula (B) in the presence of a base:

wherein R1, R2, ^m , X, v, Y, n and Z are as defined above, and T can be ^hydrogen or a halogen selected from Cl, Br or I, provided that when T is hydrogen, both n and m Both are 0;

wherein Q, t, W are as defined above, and L is hydroxyl (-OH).

Useful bases are any suitable bases capable of removing hydrogen halides in nucleophilic substitution reactions, such as tertiary amines. Generally suitable bases include, but are not limited to, triethylamine or N-methylimidazole.

Any suitable amount of base may be used, including from about 1 to about 10 equivalents, or from about 1 to about 5 equivalents, based on the amount of the compound of Formula A.

The method can optionally be carried out in a solvent. Solvents that can be used include, but are not limited to: chloroform, dichloromethane, tetrahydrofuran, acetonitrile, toluene, or mixtures thereof.

The process can be carried out at temperatures ranging from about -5°C to about 110°C.

Another method that can be used to make hybrid flame retardant compounds of formula (I) involves making compounds of formula (A) (wherein R ¹ , R ² , m, X, v, Y, n and Z are as above) in the presence of a base By definition, T is hydroxy (-OH) and m cannot be 0) is reacted with a compound of formula (B) wherein Q, t, W are as defined above and L is a halogen selected from Cl, Br or I.

A base that can be used is an alkali metal base, such as alkali metal alkoxides, alkali metal amides and alkali metal alkyl amides. Examples of bases that can be used include, but are not limited to, sodium methoxide, potassium methoxide, sodium ethoxide, potassium ethoxide, sodium tert-butoxide, potassium tert-butoxide, lithium diisopropylamide, and mixtures thereof.

The method can optionally be carried out in a solvent. Solvents that can be used include, but are not limited to, tetrahydrofuran, acetonitrile, toluene, xylene; N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide, or mixtures thereof.

The process can be carried out at a temperature ranging from about -5°C to about 75°C.

Preferably, the compound of formula (I) should be greater than 95% pure, more preferably 98% or most preferably 99% pure when combined with a polyester.

In the present invention, "thermoplastic polyester resin" is defined as a polyester based on at least one aliphatic or aromatic dihydroxy compound and at least one aromatic dicarboxylic acid. The thermoplastic polyester used in the various embodiments is not limited and can vary. Particularly preferred polyesters are polybutylene terephthalate (often abbreviated as PBT), polyethylene terephthalate (often abbreviated as PET) and polyethylene naphthalate (often abbreviated as PET). PEN) or any combination of these. The term "thermoplastic polyester" also includes thermoplastic copolyester elastomers such as, but not limited to, copolyetheresters (often abbreviated as COPES or TPE-E). Other polyesters not specifically described are also encompassed by these embodiments and can be combined with the hybrid flame retardant systems described above to produce the flame retardant polyesters of the present invention. Products of this type are for example (BASF, PBT) and (DSM, TPE-E).

The total content of hybrid flame retardant ingredients according to the present invention can vary between embodiments of the flame retardant polymer material (hereinafter also simply referred to as "composition") and can vary based on the desired properties of the flame retardant polymer material.

For example, in some embodiments, especially in the case of polymeric materials in particulate or molded form, the total content of flame retardant ingredients is preferably less than 30% by weight of the total weight of the composition, more preferably less than 30% by weight of the total composition. 25% by weight of the total weight of the composition, most preferably less than 20% by weight of the total weight of the composition, such that the mechanical and electrical properties are satisfactory for most desired applications. However, in order to achieve satisfactory flame retardant properties, the total content of flame retardant components is preferably not less than 14% by weight based on the total weight of the composition.

In other embodiments, especially in the case of polymeric materials in the form of fibers, the total content of flame retardant ingredients is preferably less than 15% by weight of the total weight of the composition, more preferably less than 5% by weight of the total weight of the composition 10% by weight, even more preferably less than 7% by weight of the total weight of the composition. However, in order to achieve satisfactory flame retardant properties, the total content of flame retardant ingredients is preferably higher than 5% by weight of the total weight of the composition.

It will be appreciated that the flame retardant polymeric material may include additional additives to provide, for example, color, or to improve one or more properties exhibited by the flame retardant polyester. Examples of such additional additives include, but are not limited to, the following: fire resistance additives, processing aids, thermal and processing stabilizers, UV stabilizers, anti-drip agents (such as but not limited to PTFE (polytetrafluoroethylene)), Pigments, dispersants, nucleating agents and other additives commonly used with polyester or polyester fibers. Such additives are typically included in commercially available polymer resins.

In one embodiment, the flame retardant polymer material further comprises a nitrogen-based flame retardant agent as a second flame retardant ingredient. Such nitrogen-based flame retardant agents are generally known and may include, but are not limited to, symmetrical triazine derivatives, complexes and condensation products with high nitrogen content. Particularly suitable nitrogen-based flame retardant agents are those which have suitable thermal stability allowing them to be melt processed at temperatures in excess of 200°C. In addition, the nitrogen-based flame retardant agent must be compatible with the polyester resin as well as with other additive ingredients used in the present invention. In addition, they should not migrate to the surface when incorporated into the polyester resin, they should be available in a fine particle size distribution suitable for melt processing, and they should not lead to discoloration or odor.

Description of drawings

The above and other features and objects of the present invention, as well as the manner in which they are achieved, will become more apparent and the invention itself will be better understood by reference to the following description of various embodiments of the invention considered in conjunction with the accompanying drawings, wherein:

Figure 1 shows products and DSC curve for 622+ Example 1 (14 wt%).

specific implementation

Example

The following examples illustrate the invention. It should be understood, however, that the invention described herein and recited in the claims is not intended to be limited by the details of the following examples.

Example 1

Synthesis of DOPO-PEPA

In this example, 500 g of 9,10-dihydro-9-oxa-phosphaphenanthrene-10-oxide (DOPO) and 458 g of pentaerythritol phosphate alcohol (PEPA) were placed in 1.5 L of dichloromethane (DCM) middle. To this stirring suspension was added 221 mL of N-methylimidazole (NMI) followed by dropwise addition of 248 mL of carbon tetrachloride ( _CCl4 ) over 1 hour. During the addition of _CCl , the temperature was maintained between 15-20 °C. Subsequently, the reaction mixture was refluxed for 6 hours. After cooling, the dichloromethane was distilled under vacuum and the product was precipitated out of water (2 L). After stirring for 3 hours, the product was filtered off as a white powder and dried under vacuum at 60°C to constant weight, yielding 744 g (82%) of DOPO-PEPA.

Melting point: mp=222°C (based on DSC, heating rate=5°C min ⁻¹ )

Thermal stability: T _5% = 338°C; T _63.% = 700°C

Phosphorus content: 15.71% by weight

¹ H-NMR, δ (ppm): 3.98-4.09 (m, 2H); 4.48 (d, =6.5Hz,); 7.34-7.40 (m, 2H), 7.51 (t, =7.7Hz, 1H); 7.65 (dt, J=3.8Hz, J=7.4Hz, 1H); 7.85-7.95(m, 2H); 8.20-8.27(m, 2H)

¹³ C-NMR, δ (ppm): 37.48, 61.87, 75.02, 119.95, 120.65, 121.92, 124.86, 125.39, 126.03, 128.91, 130.03, 131.06, 134.41, 136.35, 148.87.

³¹ P-NMR, δ (ppm): -7.18; 10.96.

Example 2

Synthesis of DOPS-PEPA

In this example, a suspension of 10 g 6-chloro-6H-dibenzo[c,e][1,2]oxophosphine (DOPCl) and 1.6 g _S8 in 100 mL toluene was heated to reflux 5 hours. After it was cooled to room temperature, 3.7 mL of N-methylimidazole (NMI) was added, followed by 8.4 g of pentaerythritol phosphate alcohol (PEPA). The temperature was maintained between 15-20°C during the addition. Subsequently, the reaction mixture was refluxed for 3 hours. After cooling to room temperature, the precipitated product was filtered off, washed with water (2 x 300 mL) and alcohol (2 x 300 mL). The obtained white powder was dried under vacuum at 60°C to constant weight, yielding 12.3 g (70%) of DOPS-PEPA.

Melting point: mp=200°C (based on DSC, heating rate=5°C min ⁻¹ )

Thermal stability: T _5% = 296°C; T _64.% = 700°C

Phosphorus content: 15.10% by weight

¹ H-NMR, δ (ppm): 3.99-4.09 (m, 2H); 4.33-4.42 (m,); 7.36-7.41 (m, 2H), 7.52 (t, =8.0Hz, 1H); 7.63-7.67 (m, 1H); 7.85 (t, = 8.0Hz, 1H); 7.95-8.02 (m, 1H), 8.18-8.22 (m, 2H)

¹³ C-NMR, δ (ppm): 37.28, 61.83, 74.94, 119.96, 122.24, 124.73, 125.10, 125.58, 126.03, 128.93, 130.81, 131.02, 134.13, 134.35, 148.77.

³¹ P-NMR, δ (ppm): -7.27; 77.03.

Examples 3 and 4

Flame retardant TPE-E (Arnitel )

Melt Processing:

Various preparations were made on a co-rotating twin-screw extruder (Haake Polylab OS, type PTW24/40, Germany) with a screw diameter of 24 mm and an L/D ratio of 40. combination. Dosing of materials was performed using a gravity feed system (Three Tec, Switzerland). All compositions were processed at the same screw speed. The measured temperature of the melt was 230°C for all formulations. The composite melt was passed through a nozzle, cooled to room temperature in a water bath and cut into pellets. The granules were dried in a vacuum oven at 100°C for 12 hours. The analyzed particles were conditioned at 50% relative humidity for 72 hours. The resulting compound is as follows:

Example 3: Arnitel With 18 wt% DOPO-PEPA (Example 1) (2.8 wt% P content), mp=224°C.

Example 4: Arnitel With 14 wt% DOPO-PEPA (Example 1) (2.2 wt% P content) and 4 wt% Melapur MC 50 (melamine cyanurate), mp=224°C.

Comparative Example 5: Arnitel Without flame retardant additives (0 wt% P content), mp=218°C.

Comparative Example 6: Arnitel Contains halogenated flame retardant additives (0 wt% P content), mp=226°C.

Comparative Example 7: Arnitel With nitrogen-based flame retardant additive (0 wt% P content), mp=216°C.

ASTM D3801UL94 – Vertical Burning Test

The dried pellets were compression molded into 1 mm thick plates and cut to the required dimensions (125 ± 5 mm long, 13.0 ± 0.5 mm wide) for ASTM D3801 UL94 - Vertical Flammability Test (V-0, V-1 or V-2) ).

Table 1. UL94 Vertical Burning Test

combination grade Comparative Example 5 No grade Comparative Example 6 V2 Comparative Example 7 V2 Example 3 V0 Example 4 V0

Differential Scanning Calorimetry (DSC)

Differential scanning calorimetry measurements were performed to evaluate recipe (Figure 1). The first heating cycle (using a heating rate of 5°C min ⁻¹ ) was used to evaluate the melting points of the compounds as reported above. After cooling at a cooling rate of 10°C min ^-1 , the formulation was reheated at a heating rate of 10°C min ^-1 . In the second heating cycle, only the composition of Example 3 showed the same melting point as the original TPE (Comparative Example 5). The decrease in the melting temperature of the thermoplastic composition in the second heating cycle strongly suggests a deterioration in the molecular weight of the thermoplastic segment and thus a decrease in its desired mechanical and physical properties. These measurements show good compatibility and no negative effects of the additive of Example 1 for the polymer matrix. in view of The composition is mainly used in the automotive industry for under-hood applications and its resistance to elevated temperatures is important from a recyclability perspective.

Example 8

flame retardant PET fiber

PET pellets with a viscosity of 1.40 g cm ^-3 ready for spinning (ready-to-spin) were premixed with 5 wt% of the hybrid flame retardant from Example 1 and passed through A hopper containing a single screw extruder with a diameter of 13 mm and a length to diameter ratio (L/D) of 25 was introduced into the spinneret. A monofilament spinneret with a diameter of 0.5 mm and an aspect ratio (L/D) of 4 was used. The PET composition was spun with a melt temperature of 270° C. and a winding speed of 1650 m min ⁻¹ . The monofilament PET composition obtained at a draw ratio of 5.5 had a diameter of Φ=59 μm and a linear fiber density of 36 dtex. The obtained flame retardant PET fibers (Example 8) had a corresponding P content of 0.8% by weight, while Comparative Example 9 was prepared as a control example without the addition of a flame retardant.

Table 2. Physical properties of flame retardant PET fibers Example 8 and Comparative Example 9

To evaluate flame resistance, the PET fibers were woven into fabrics at a density of 0.13±0.03 g cm ⁻² . Five samples of 10 cm length were cut from each example with an average weight of 1 ± 0.02 g. The 100±5mm long tightly rolled samples were subjected to vertical burn testing according to the test procedure and material classification described in ASTM D3801 UL94 - Vertical Burn Test (V-0, V-1 or V-2) and the results listed in Table 2.

Example 10

Flame Retardant PBT

Various preparations were made on a co-rotating twin-screw extruder (Haake Polylab OS, type PTW24/40, Germany) with a screw diameter of 24 mm and an L/D ratio of 40. combination. Dosing of materials was performed using a gravity feed system (Three Tec, Switzerland). All compositions were processed at the same screw speed. The composite melt was passed through a nozzle, cooled to room temperature in a water bath and cut into pellets. The granules were dried in a vacuum oven at 80°C for 12 hours. The analyzed particles were conditioned at 50% relative humidity for 72 hours.

The resulting compound is as follows:

Example 10: With 20 wt% DOPO-PEPA (Example 1) (3.2 wt% P content) and 4.5 wt% Melapur MC 50 (melamine cyanurate).

Comparative Example 11: No flame retardant additives (0 wt% P content).

ASTM D3801UL94 – Vertical Burning Test

The dried pellets were compression moulded into 1 mm thick plates and cut to the required dimensions (125 ± 5 mm long, 13.0 ± 0.5 mm wide) for ASTM D3801 UL94 - Vertical Flammability Test (V-0, V-1 or V-2) ).

Table 1. UL94 Vertical Burning Test

combination grade Comparative Example 11 No grade Example 10 V0

Claims (15)

1. flame-retardant compound, the structure with Formulas I:

Wherein:

R¹And R²It independently is hydrogen, C₁-C₆Alkyl ,-P (O) (OR³)₂、-P(O)OR³R⁴Or-P (O) R³ ₂, wherein R³And R⁴Independently For C₁-C₄Alkyl, C₆-C₁₂Aryl, C₇-C₁₅Aralkyl or C₇-C₁₅Alkaryl；Or R¹And R²It is formed together unsaturated cyclic ring, The cyclic rings are optionally replaced by alkyl group；

Each k independently 1 to 2 integer；

Each X independently is oxygen (O) or sulphur (S)；

V is 0 or 1；

Each Y independently is C₁-C₄Alkylidene, C₆Arlydene, C₇-C₁₅Sub- aralkyl, C₇-C₁₅Alkarylene, oxygen (O), nitrogen (NR), Wherein R is H or C₁-C₄Alkyl；

N is 0,1 or 2, and condition is the n 1 when Y is oxygen (O) or nitrogen (NR)；

Each Z independently is C₁-C₄Alkylidene, C₆Arlydene, C₇-C₁₅Sub- aralkyl or C₇-C₁₅Alkarylene；

M independently is 0,1 or 2；Condition is when Y is oxygen (O) or nitrogen (N), and m cannot be 0；

Each Q independently is C₁-C₄Alkylidene；

The integer that t is 1 to 2；

W is oxygen (O) or sulphur (S).

2. flame-retardant compound according to claim 1, is selected from:

-DOPO-PEPA；With

-DOPS-PEPA。

3. the polymer material with improved flame resistance, it includes at least one thermoplastic polymer resins, at least one root According to the flame-retardant compound of claims 1 or 2 and optionally comprising any conventional additive.

4. polymer material according to claim 3, wherein the thermoplastic polymer resin is thermoplastic polyester.

5. it is fire-retardant as second to further include the anti-flammability reagent based on nitrogen according to the polymer material of claim 3 or 4 Ingredient.

6. being particle form or molded form according to the polymer material of claim 3 or 4.

7. polymer material according to claim 6, wherein the total content of flame-retardant composition (I) is the total weight of the composition 14% to 30% weight.

8. being fibers form according to the polymer material of claim 3 or 4.

9. polymer material according to claim 8, wherein the total content of flame-retardant composition (I) is the total weight of the composition 5% to 20% weight.

10. according to the polymer material of claim 3 or 4, wherein the flame-retardant compound is as surface layer deposition.

11. polymer material according to claim 6, further include the anti-flammability reagent based on nitrogen as second it is fire-retardant at Point.

12. polymer material according to claim 7, further include the anti-flammability reagent based on nitrogen as second it is fire-retardant at Point.

13. polymer material according to claim 8, further include the anti-flammability reagent based on nitrogen as second it is fire-retardant at Point.

14. polymer material according to claim 9, further include the anti-flammability reagent based on nitrogen as second it is fire-retardant at Point.

15. the method for manufacturing flame-retardant compound according to claim 1, the method includes formulas in the presence of base (A) Compound is reacted with the compound of formula (B):

Wherein:

a)R¹、R², m, X, v, Y, n and Z it is as defined above, T can be hydrogen or the halogen selected from Cl, Br or I, condition be when T be hydrogen When, both n and m are 0；Wherein Q, t, W are as defined above, and L is hydroxyl (- OH)；Or

b)R¹、R², m, X, v, Y, n and Z it is as defined above, T is that hydroxyl (- OH) and m are different from 0, and wherein Q, t, W are as defined above And L is the halogen selected from Cl, Br or I.